CN105521776A - Composite metal oxide Bi4Ti3O12Nanocrystalline and preparation method thereof - Google Patents
Composite metal oxide Bi4Ti3O12Nanocrystalline and preparation method thereof Download PDFInfo
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- CN105521776A CN105521776A CN201410514535.0A CN201410514535A CN105521776A CN 105521776 A CN105521776 A CN 105521776A CN 201410514535 A CN201410514535 A CN 201410514535A CN 105521776 A CN105521776 A CN 105521776A
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- metal oxide
- composite metal
- nanocrystalline
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- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 24
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims description 7
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002159 nanocrystal Substances 0.000 abstract 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention discloses a composite metal oxide Bi4Ti3O12A method for preparing a nanocrystal. Using KOH solution as mineralizer by adding Ti (OC)4H9)4Regulating the state of the mixed solution, and preparing the composite metal oxide Bi in a spatial network shape by a hydrothermal method4Ti3O12And (4) nanocrystals. The method is simple, no surfactant is required to be added or the raw materials are not required to be reprocessed, and the Bi is obtained only by taking bismuth nitrate and tetrabutyl titanate as the raw materials4Ti3O12A nanocrystal; the method has no pollution to the environment, does not use any organic solvent in the reaction process, and simultaneously produces waste liquid without pollution to the environment; to produce Bi4Ti3O12The nanocrystalline is a uniform spatial network structure, is positioned in a nanoscale, has a larger specific surface area, and is beneficial to improving the catalytic performance of the nanocrystalline.
Description
Technical field
The present invention relates to a kind of Bi-Ti system composite metal oxide nanocrystalline and preparation method thereof, particularly a kind of spatial networks composite metal oxide Bi
4ti
3o
12and preparation method thereof, belong to field of inorganic nano-material preparation.
Background technology
In recent years, the application of Photocatalitic Technique of Semiconductor in Environment control and photolysis water hydrogen etc. obtains and studies very widely.Wherein, TiO
2because it is to chemistry and biological nontoxicity, inertia, high stability and advantage of low cost, be seen as one of semiconductor light-catalyst having potential using value most.But due to TiO
2two inherent shortcomings: greater band gap, can only be less than the ultraviolet excitation of 386.5nm by wavelength, and accounts for the visible ray reaching ground surface sunlight gross energy 90% and can not be utilized; TiO
2the electronics that middle optical excitation produces and hole are very easy to compound, and its photo-quantum efficiency is extremely low, and its photocatalytic activity is subject to great impact.The research of head it off mainly concentrates on two aspects at present: to TiO
2carry out modification or development of new semiconductor light-catalyst, require that it can be activated by visible ray, and there is high photocatalytic activity.Composite metal oxide Bi
4ti
3o
12pass through Bi
2o
3with TiO
2carry out composite modified, make it have stronger photocatalysis performance and good ferroelectric properties.
At present, the people such as DanielThomazini with Solid phase synthesis Bi
4ti
3o
12, but its product is larger sheet aggregate, thickness is large, reaction difficulty, is difficult to promote; The people such as XueLin adopt bismuth nitrate, butyl titanate to be that raw material adopts hydro-thermal method successfully to synthesize spherical Bi
4ti
3o
12, but its particle diameter reaches micron order, and specific area is less, has had a strong impact on its photocatalysis performance; The people such as ZhiwuChen are with bismuth nitrate, butyl titanate for raw material, and by adding acetic acid, ethanol carries out process to raw material and obtain sheet Bi
4ti
3o
12, because its Making programme is more complicated, make it be difficult to promote.
Summary of the invention
The object of the present invention is to provide a kind of spatial networks composite metal oxide Bi
4ti
3o
12nanocrystalline and preparation method thereof.
The technical solution realizing the object of the invention is: a kind of composite metal oxide Bi
4ti
3o
12nanocrystalline, described Bi
4ti
3o
12nanocrystalline is space net structure.
Soft chemical method is utilized to prepare the above-mentioned composite metal oxide Bi with unique morphology
4ti
3o
12nanocrystalline method, comprises the following steps:
Step one: by Ti (OC
4h
9)
4be dissolved in bismuth nitrate or bismuth chloride solution;
Step 2: drip KOH solution until solution ph is more than 13 in step one solution;
Step 3: step 2 solution is placed in reactor and reacts at 180 DEG C;
Step 4: reaction terminates rear washing and namely obtains netted composite metal oxide Bi
4ti
3o
12nanocrystalline.
Bi in step one
3+with Ti
4+mol ratio is 4:3.
The molar concentration of the KOH solution described in step 2 is 10mol/L.
Reaction time described in step 4 is 24h.
The present invention has following remarkable advantage:
1, method is simple, without the need to adding any surfactant or carrying out reprocessing to raw material, only with bismuth nitrate and butyl titanate for namely raw material obtains Bi
4ti
3o
12nanocrystalline;
2, environmentally safe, does not use any organic solvent in course of reaction, produces waste liquid simultaneously and does not pollute environment yet;
3, obtained Bi
4ti
3o
12nanocrystalline is homogeneous space net structure, is positioned at nanoscale, has larger specific area, is conducive to the raising of its catalytic performance.
Accompanying drawing explanation
Fig. 1 the present invention utilizes five water bismuth nitrates and butyl titanate to prepare under hydrothermal conditions to have cancellated composite metal oxide Bi
4ti
3o
12nanocrystalline schematic flow sheet.
Fig. 2 is the cancellated composite metal oxide Bi of the embodiment of the present invention 1 and 2
4ti
3o
12transmission electron microscope picture (a) embodiment 1 of nanocrystalline sample; (b) embodiment 2.
Fig. 3 is Bi obtained by comparative example 1 and 2 of the present invention
4ti
3o
12transmission electron microscope picture (a) comparative example 1 of nanocrystalline sample; (b) comparative example 2.
Fig. 4 is that Visible Light Induced Photocatalytic figure (a) using the cancellated composite metal oxide of the embodiment of the present invention 1 and 2 as catalyst is using embodiment 1 product as catalyst; B () is using embodiment 2 product as catalyst.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Composition graphs 1, the present invention utilizes five water bismuth nitrates or bismuth chloride and butyl titanate to prepare the composite metal oxide Bi with space net structure under hydrothermal conditions
4ti
3o
12nanocrystalline method, comprises the following steps:
Step one: by Ti (OC
4h
9)
4be dissolved in bismuth nitrate or bismuth chloride solution;
Step 2: drip KOH solution until solution ph is more than 13 in step one solution;
Step 3: step 2 solution is placed in reactor and reacts at 180 DEG C;
Step 4: reaction terminates rear washing and namely obtains netted composite metal oxide Bi
4ti
3o
12nanocrystalline.
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described in detail:
Embodiment 1:
Step one: add 2mmol five water bismuth nitrate in 15ml deionized water solution, stirs, obtains uniform solution, then by 1.5mmolTi (OC
4h
9)
4be dissolved in step one gained solution;
Step 2: drip 10mol/LKOH solution in step one solution, makes its pH value be 13.1;
Step 3: step 2 solution is placed in reactor reacts 24h at 180 DEG C;
Step 4: reaction terminates rear washing and namely obtains spatial networks composite metal oxide Bi
4ti
3o
12nanocrystalline.
The transmission electron microscope picture of products therefrom is as shown in Fig. 2 (a), and product defines the network structure be made up of little stub, and spatial joint clearance is comparatively large, disperses more even.As can be seen from photocatalytic degradation Fig. 4 (a), use 20mg catalyst to degrade under 500W xenon lamp irradiates 50ml10mg/L methyl orange, after 30min is penetrated in illumination, methyl orange is degradable.
Embodiment 2:
Step one: add 2mmol bismuth chloride in 15ml deionized water solution, stirs, obtains uniform solution, then by 1.5mmolTi (OC
4h
9)
4be dissolved in step one gained solution;
Step 2: drip 10mol/LKOH solution in step one solution, makes its pH value be 13.1;
Step 3: step 2 solution is placed in reactor reacts 24h at 180 DEG C;
Step 4: reaction terminates rear washing and namely obtains spatial networks composite metal oxide Bi
4ti
3o
12nanocrystalline.
The transmission electron microscope picture of products therefrom is as shown in Fig. 2 (b), and product defines the network structure be made up of little stub, and spatial joint clearance is less, arranges tightr.As can be seen from photocatalytic degradation Fig. 4 (b), 20mg catalyst is used to degrade under 500W xenon lamp irradiates 50ml10mg/L methyl orange, methyl orange degradation 90% when 50min is penetrated in illumination.
Comparative example 1:
Step one: add 2mmol five water bismuth nitrate in 15ml deionized water solution, stirs, obtains uniform solution, then by 1.5mmolTi (OC
4h
9)
4be dissolved in step one gained solution;
Step 2: drip 1mol/LKOH solution in step one solution, makes its pH value be 13.1;
Step 3: step 2 solution is placed in reactor reacts 24h at 180 DEG C;
Step 4: reaction terminates rear washing and namely obtains Bi
4ti
3o
12nanocrystalline.
The transmission electron microscope picture of products therefrom is as shown in Fig. 3 (a), product major part is made up of particle, part defines club shaped structure, can think to react and not exclusively caused, this shows under pH mono-stable condition, be distinct using the KOH of high concentration as the KOH of mineralizer and low concentration, the KOH of high concentration is conducive to the formation of rod.
Comparative example 2:
Step one: add 2mmol five water bismuth nitrate in 15ml deionized water solution, stirs, obtains uniform solution, then by 1.5mmolTi (OC
4h
9)
4be dissolved in step one gained solution;
Step 2: drip 10mol/LKOH solution in step one solution, makes its pH value be 13.1;
Step 3: step 2 solution is placed in reactor reacts 12h at 180 DEG C;
Step 4: reaction terminates rear washing and namely obtains Bi
4ti
3o
12nanocrystalline.
The transmission electron microscope picture of products therefrom is as shown in Fig. 3 (b), product does not have regular shape, but can find out and have part or to define club shaped structure, this shows the impact of reaction time on product, in reaction beginning after 12 hours, product is not shaped completely, can predict, along with the prolongation of time, the space net structure be made up of rod can be formed gradually.
Claims (5)
1. a composite metal oxide Bi
4ti
3o
12nanocrystalline, it is characterized in that, described Bi
4ti
3o
12nanocrystalline is space net structure.
2. prepare composite metal oxide Bi as claimed in claim 1 for one kind
4ti
3o
12nanocrystalline method, is characterized in that, comprises the following steps:
Step one: by Ti (OC
4h
9)
4be dissolved in bismuth nitrate or bismuth chloride solution;
Step 2: drip KOH solution until solution ph is more than 13 in step one solution;
Step 3: step 2 solution is placed in reactor and reacts at 180 DEG C;
Step 4: reaction terminates rear washing and namely obtains netted composite metal oxide Bi
4ti
3o
12nanocrystalline.
3. according to claim 2ly prepare composite metal oxide Bi
4ti
3o
12nanocrystalline method, is characterized in that, Bi in step one
3+with Ti
4+mol ratio is 4:3.
4. according to claim 2ly prepare composite metal oxide Bi
4ti
3o
12nanocrystalline method, is characterized in that, the molar concentration of the KOH solution described in step 2 is 10mol/L.
5. according to claim 2ly prepare composite metal oxide Bi
4ti
3o
12nanocrystalline method, is characterized in that, the reaction time described in step 4 is 24h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514535.0A CN105521776A (en) | 2014-09-29 | 2014-09-29 | Composite metal oxide Bi4Ti3O12Nanocrystalline and preparation method thereof |
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|---|---|---|---|
| CN201410514535.0A CN105521776A (en) | 2014-09-29 | 2014-09-29 | Composite metal oxide Bi4Ti3O12Nanocrystalline and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
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Family
ID=55764499
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106915771A (en) * | 2017-02-27 | 2017-07-04 | 江苏大学 | One kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template |
| CN109513437A (en) * | 2018-12-13 | 2019-03-26 | 兰州理工大学 | Activate the preparation method of bismuth titanates and the purposes as semiconductor light-catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097216A (en) * | 2011-03-11 | 2011-06-15 | 河南大学 | Novel photoanode material Bi4Ti3O12 of dye sensitized solar cells |
| CN102260076A (en) * | 2011-04-30 | 2011-11-30 | 桂林电子科技大学 | X8R ceramic capacitor ceramic material and preparation method thereof |
| CN104211116A (en) * | 2014-08-26 | 2014-12-17 | 浙江大学 | Preparation method of Bi4Ti3O12 single-crystal nanorod and Bi4Ti3O12 single-crystal nanorod product |
-
2014
- 2014-09-29 CN CN201410514535.0A patent/CN105521776A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097216A (en) * | 2011-03-11 | 2011-06-15 | 河南大学 | Novel photoanode material Bi4Ti3O12 of dye sensitized solar cells |
| CN102260076A (en) * | 2011-04-30 | 2011-11-30 | 桂林电子科技大学 | X8R ceramic capacitor ceramic material and preparation method thereof |
| CN104211116A (en) * | 2014-08-26 | 2014-12-17 | 浙江大学 | Preparation method of Bi4Ti3O12 single-crystal nanorod and Bi4Ti3O12 single-crystal nanorod product |
Non-Patent Citations (3)
| Title |
|---|
| FANG WANG，ET AL: "Shape-controlled hydrothermal synthesis of ferroelectric Bi4Ti3O12 nanostructures", 《CRYSTENGCOMM》 * |
| XUE LIN，ET AL: "Influence of pH Value on Photocatalytic Activity of Bi4Ti3O12 Crystals Obtained by Hydrothermal Method", 《CHINESE JOURNAL OF CHEMICAL PHYSICS》 * |
| YANHUI SHI，ET AL: "Hydrothermal synthesis and characterization of Bi4Ti3O12", 《MATERIALS LETTERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106915771A (en) * | 2017-02-27 | 2017-07-04 | 江苏大学 | One kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template |
| CN106915771B (en) * | 2017-02-27 | 2018-06-01 | 江苏大学 | One kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template |
| CN109513437A (en) * | 2018-12-13 | 2019-03-26 | 兰州理工大学 | Activate the preparation method of bismuth titanates and the purposes as semiconductor light-catalyst |
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